Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
  • C07C213/06—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton from hydroxy amines by reactions involving the etherification or esterification of hydroxy groups
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
  • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
  • B01J2531/26—Zinc
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/0215—Sulfur-containing compounds
  • B01J31/0225—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts
  • B01J31/0227—Sulfur-containing compounds comprising sulfonic acid groups or the corresponding salts being perfluorinated, i.e. comprising at least one perfluorinated moiety as substructure in case of polyfunctional compounds
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
  • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
  • B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts

Definitions

• the presently described technology relates generally to a method for producing esteramines through transesterification or esterification processing between alkanolamines and alkyl esters or fatty acids. More specifically, the present technology provides methods for decreasing the reaction time and/or lowering the reaction temperature needed to react alkanolamines and fatty acid alkyl esters, fatty acids, or mixtures thereof through utilization of zinc catalysts.
• Sodium or potassium alkoxides e.g., methoxides
• alkyl esters for transesterification reaction processing. Such processes are seriously inhibited, however, by moisture and/or acidic impurities.
• These types of alkoxides also produce resultant transesterified products that, in many instances, exhibit the viscosity of a gel, due to side reactions.
• Potassium hydroxide is often used to catalyze the reaction between triglycerides and triethanolamme.
• reaction is still very slow and is believed by those skilled in the art to be due, in part, to the potassium hydroxide immediately reacting with acidic impurities during reaction processing to generate water and other potassium salts, which may, or may not, be of any use as catalysts.
• Titanium catalysts sold commercially under the brand name TYZOR® have also been used to catalyze the reaction of triethanolamme and fatty acid. Such titanium catalysts, however, also have several drawbacks. In particular, titanium catalysts tend to form titanium precipitates in solution. Residual titanium catalysts can also interfere with product stability and result in a poorly colored product that may require further bleaching. In addition, when titanium catalysts are used with triethanolamme and fatty acid, the resulting ratios of monester, diester and triester esteramines are not in line with established product specifications. Further, it is known that the activity of titanium catalysts are negatively impacted by amines in the absence of carboxylic acids. This affect, is a hindrance when a carboxylic acid feed is replaced by an alkyl ester feed such as methylester, in conducting the reaction to produce the esteramine.
• the presently described technology provides a method for decreasing the reaction time between an alkanolamine and a fatty acid alkyl ester, a fatty acid, or a mixture thereof by utilizing a divalent zinc catalyst.
• the transesterification or esterification reaction can proceed to completion substantively faster than, and in some cases twice as fast as when conventional catalysts are used.
• Suitable alkanolamines include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, alkyldiethanolamines, alkyldiisopropanolamines, dialkylmonoethanolamines, dialkylmonoisopropanolamines, and combinations thereof.
• Preferred alkanolamines for the presently described technology are dimethylethanolamine (DMEA) methydiethanolamine (MDEA) and triethanolamine (TEA).
• Suitable fatty acid alkyl esters and fatty acids include triglycerides, vegetable oils, fatty acid methylesters, fatty acid ethylesters, stearic acid, tallow fatty acid, derivatives thereof, and combinations thereof.
• the divalent zinc catalyst is added in a usable form to the reaction mixture so that the zinc can be soluble in order for homogeneous catalysis to occur.
• the divalent zinc catalyst is in the form of zinc oxide, zinc carbonate, or zinc diphosphinate.
• the divalent zinc is in the form of a zinc salt.
• the resulting esteramines of the present technology can be derivitized with a quaternizing agent, such as, for example, methyl chloride or dimethyl sulfate in order to produce a fabric softener or anti-static agent.
• a quaternizing agent such as, for example, methyl chloride or dimethyl sulfate
• Other quaternizing agents can also be used, such as epichlorohydrin, or derivatives thereof, such as 3-chloro-2-hydroxypropanesulfonate, sodium salt.
• the presently described technology relates generally to a method for producing esteramines through the transesterification or esterification reaction of alkanolamines and alkyl esters, fatty acids, or mixtures thereof. More specifically, the present technology provides a method for decreasing the reaction time between alkanolamines (e.g., triethanolamine) and fatty acid alkyl esters (e.g., triglycerides, vegetable oils, fatty acid methylesters, fatty acid ethylesters, etc.), fatty acids, or mixtures thereof.
• alkanolamines e.g., triethanolamine
• fatty acid alkyl esters e.g., triglycerides, vegetable oils, fatty acid methylesters, fatty acid ethylesters, etc.
• the presently described technology utilizes a divalent zinc catalyst in at least one esterification or transesterification reaction to produce an esteramine.
• divalent zinc is meant zinc in its 2 oxidation state.
• the divalent zinc should be added in a usable form to the reaction mixture so that the zinc can become soluble in order for homogeneous catalysis to occur.
• the zinc catalyst can be added in the form of zinc oxide or any other zinc compound which can supply a soluble form of divalent zinc to the reaction mixture, these include but are not limited to zinc salts such as zinc carbonate or zinc triflate.
• the zinc oxide is then rapidly converted by the molten carboxylic acid to zinc dicarboxylate, or if stearic acid is used as the fatty acid, the zinc oxide is converted to zinc distearate.
• Zinc salts of phosphinic acid such as zinc diphosphinate can also be used as the catalyst.
• Zinc diphosphinate can be made in situ or, alternatively from a separate reaction of zinc oxide and phosphinic acid.
• Other zinc catalysts such as zinc carbonate and zinc triflate, can also be used.
• the divalent zinc should be added in the form of a soluble salt, since zinc oxide or zinc carbonate are not sufficiently soluble in this starting mixture to generate a workable divalent homogeneous zinc catalyst.
• Suitable zinc salts for use as the catalyst for the alkyl ester transesterification reaction of fatty alkyl ester and alkanolamine include zinc acetate or zinc diphosphinate.
• the divalent zinc catalyst of the present technology can unexpectedly improve esterification or transesterification speed/reaction time.
• the esterification or transesterification reaction can proceed to completion, on average, twice as fast as when other catalysts are used in place of divalent zinc when compared on a molar basis.
• the divalent zinc catalysts of the present technology can also visually improve the color of the resultant esteramine materials such that a subsequently quaternized material can be of improved color also. This can, for example, make an additional bleaching step unnecessary when producing products according to the present technology.
• the divalent zinc catalysts can produce esteramine products that are free of precipitates and that also have superior storage stability compared to esteramine products prepared by using other catalysts.
• a further advantage of the divalent zinc catalysts of the present technology is that, with respect to the reaction of triethanolamine and fatty acid, the resulting mole ratios of monoester, diester and triester esteramines in the final product mixture are consistent with the established product specifications for esteramines that were obtained from the well established Bronsted acid catalysis.
• esteramines are composed of a mixture of monoesterified, diesterified, and triesterified esteramines. This mixture is made possible due to the fact that triethanolamine contains three identical alcohols, each of which can react with a fatty acid or fatty alkyl ester to generate the ester bonds.
• the divalent zinc catalyst of the present technology is employed instead of a traditional acid or base catalyst, the final product mixtures have an identical mixture composition of monoester, diester and triester esteramines, as compared to mixtures obtained from traditional Bronsted catalysts, yet the overall esterification reaction proceeds at a much faster rate.
• the resulting esteramines are composed of a mixture of monoesterified and diesterified esteramines.
• This mixture is made possible due to the fact that methyl diethanolamine contains two identical alcohols, each of which can react with a fatty acid, or fatty alkyl ester, to generate the ester bonds.
• divalent zinc is employed as the catalyst instead of a traditional Bronsted acid catalyst, the final product mixtures have an identical composition mixture of monoester and diester esteramines compared to mixtures obtained from traditional Bronsted catalysts, but the overall esterification reaction proceeds at a much faster rate.
• the divalent zinc catalysts of the present technology are also surprisingly active in the presence of moisture and/or acidic materials, which may be present in feedstocks utilized for reaction processing. This acidic material may be, for example, residual fatty acid.
• the divalent zinc catalysts of the present technology can also prevent gelling of the resultant esteramines by minimizing side reactions, which often occur when stronger bases are used to catalyze transesterification reactions.
• Another advantage of the divalent zinc catalyst of the present technology is that it does not become deactivated by amines.
• the problem with Bronsted acid catalysis in the presence of amines is that the acids quickly become deactivated due to proton transfer from the acid to the nitrogen on the amine.
• the strong nature of the acid catalysts, as compared to the weaker carboxylic acids, causes them to lose their proton preferentially to the amine, thus preventing strong acid proton availability for catalysis. This transfer makes the proton largely unavailable to perform any catalysis on the moieties which are crucial to the esterification reaction.
• catalysis by metals is possible and the metals are known to be coordinated Lewis acids.
• divalent zinc is an effective catalyst and does not become deactivated by amines. This development is a surprise, since amines are known to coordinate to divalent zinc, or metal ions in general, but this apparently does not significantly hinder the catalysis of the esterification reaction for zinc. Without being bound by theory, it is believed that divalent zinc can act as a Lewis acid without changing the pH of the reaction media.
• Divalent zinc catalysts are therefore superior to protic acids, because: 1) divalent zinc may induce multiple positive charges into reactants, while a proton can induce only a single positive charge, 2) divalent zinc can exist in neutral media not just acidic solutions, which can minimize unwanted side reactions, and 3) divalent zinc can coordinate to several electron donor atoms simultaneously, whereas a proton usually coordinates to only one donor atom.
• Suitable starting fatty acid esters for the present technology include, for example, fatty acid alkyl esters, and may contain any combination of fatty acid alkyl groups having from about 2 to about 30, alternatively from about 5 to about 25 carbon atoms.
• the fatty acid alkyl groups can be either saturated or unsaturated or partially hydrogenated.
• the ester alkyl groups i.e., the alkyl groups utilized to form esters with the fatty acid
• the ester alkyl groups may be complex or simple, and can also contain alkyl groups, with or without branching, having from about 1 to about 30, alternatively from about 1 to about 25, alternatively from about 1 to about 4 carbon atoms.
• the ester alkyl groups may contain multiple hydroxides, free or functionalized.
• suitable starting fatty acid esters include, but are not limited to, triglycerides, vegetable oils, fatty acid methylesters, fatty acid ethylesters, derivatives thereof, and combinations thereof.
• Suitable starting fatty acids for the present technology can be, for example, any alkyl acid having from about 2 to about 30, alternatively from about 5 to about 25 carbon atoms, and can be saturated or unsaturated or partially hydrogenated.
• Suitable alkanolamines for the present technology include, for example, ethanolamine, diethanolamine, triethanolamine, isopropanolamine, diisopropanolamine, triisopropanolamine, alkyldiethanolamines, alkyldiisopropanolamines, dialkyl monoethanolamines, dialkylmonoisopropanolamines, and combinations thereof.
• the alkyl groups in the alkanolamines may contain from about 1 to about 30 carbon atoms, and can be saturated or unsaturated, linear, cyclic, or aromatic.
• Preferred alkanolamines for the present technology include methyldiethanolamine and triethanolamine.
• the combined catalyst and starting materials including the alkanolamines and fatty alkyl esters can be heated to a temperature of from about 60° C to about 300°C, alternatively from about 130° C to about 190° C, alternatively from about 150° C to about 200° C.
• a temperature of from about 60° C to about 300°C alternatively from about 130° C to about 190° C, alternatively from about 150° C to about 200° C.
• the divalent zinc catalyst of the present technology can unexpectedly lower the required reaction temperature, while still keeping the reaction at a commercially viable or improved speed.
• to conduct the transesterification reaction at a lower temperature can not only save energy costs but also reduce side reactions and the amount of undesired side products.
• the esterification reaction can be conducted within one preferred temperature range. In accordance with some other embodiments of present technology, the esterification reaction can be conducted within a first preferred temperature range for a period of time, and then within another preferred temperature range for another period of time, and there can be two or more such periods.
• the molar ratio of alkanolamine and alkyl esters, fatty acids, or mixtures thereof, where the alkanolamine is in the denominator of the ratio can be from about 0.5/1 to 3/1, alternatively about 1.5/1 to about 2.0/1, alternatively about 1.7/1 to about 2.0/1, alternatively 1.7/1 to 1.75/1, alternatively about 1.88/1 to about 1.92/1.
• the divalent zinc catalysts of the present technology can be added either before or after the reaction temperature has been reached.
• the amount of catalyst contained in the reaction mixture should be an effective amount of divalent zinc metal greater than 1 ppm and calculated from the total weight of reactants, preferably from about 20 ppm to about 5000 ppm by weight, most preferably at about 100 ppm to about 200 ppm.
• the reaction occurs in the presence of an inert atmosphere such as, but not limited to, nitrogen.
• a vacuum system can be attached to the reaction system in order to remove, for example, volatile alcohols, products, or by-products during the course of the esterification or transesterification reaction.
• the divalent zinc catalyst is an improved or superior catalyst for the esterification reaction of alkanolamines with fatty carboxylic acids or carboxylic acids, and the transesterification reaction of alkanolamines with fatty alkyl esters or methyl esters or esters generally. It has also been surprisingly observed that the divalent zinc catalyst is also affected by the structure of the alkanolamines, during the course of the esterification or transesterification reactions, thus, a relative reactivity scale is as follows: polyolalkylamine »> triolalkylamine » diolalkylamine > monoalkanolamine.
• the divalent zinc is chelated by the alkanolamines, in such a way, as to better facilitate the esterification or transesterification reactions.
• the zinc catalyst could be used to catalyze the esterification reaction of (1) fatty or carboxylic acids with alcohols, or (2) fatty alkyl esters or methyl esters with alcohols.
• the zinc oxide(Sunsmart, lot#189, 0.3575 grams) was added to the fatty acid. This amount of ZnO gave a pre-reaction Zinc concentration of 125 ppm.
• the nitrogen was regulated and subsurface sparged at a rate of 175mL/min. The mixture was stirred.
• a vacuum was used to remove the excess oxygen, with the application of 80 mmHg vacuum followed by nitrogen release; this cycle was applied twice.
• the mixture was heated until a temperature of 180°C was reached.
• the majority of the water was condensed at atmospheric pressure with the help of an air cooled condenser, before 150°C was reached.
• the vacuum was applied at 83 mmHg.
• Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using 0.1002N KOH/Methanol.
• the expected free fatty acid range was 0.11-0.08 mEq/g.
• the reaction reached completion 0.75 hour after the temperature of 180°C was reached.
• the nitrogen was regulated and subsurface sparged at a rate of 175mL/min. The mixture was stirred. A vacuum was used to remove the excess oxygen, with the application of 80 mmHg vacuum followed by nitrogen release; this cycle was applied twice. The mixture was heated until a temperature of 180°C was reached.
• the mixture was stirred.
• the pre- reaction zinc content was calculated to be 105 ppm.
• the mixture was stirred.
• the nitrogen was subsurface sparged at a rate of 200ml/min. The mixture was heated until a temperature of 170°C was reached.
• the nitrogen was regulated and subsurface sparged at a rate of 200 mL/min.
• the mixture was heated until a temperature of 170°C was reached.
• the water was condensed with the help of an air cooled condenser.
• Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using O. IOOON KOH/Methanol.
• the final expected free fatty acid goal was 0.06 mEq/g.
• the reaction reached completion 4.5 hours after Tmax was reached.
• Tallow fatty acid (839.0 g, 3.05 mole) was placed into a round bottom flask at 100°C, under a blanket of nitrogen.
• Methyldiethanolamine 220.7 g, 1.91 mole was added to the flask.
• the zinc stearate was added at a loading level of 1000 ppm. This amount gave a pre-reaction Zinc concentration of about 100 ppm.
• the mixture was stirred and heated until a temperature of 190°C was reached.
• the nitrogen was regulated and subsurface sparged at a rate of between 150 mL/min and 200 mL/min.
• the water was condensed with the help of an air cooled condenser.
• a vacuum of 160 mmHg was applied when the batch acid value reached 0.35 mEq/g or less.
• Samples of crude esteramine were collected at intervals and titrated for residual fatty acid with a visual phenolphthalein endpoint using O. IOOON KOH/Methanol.
• the final expected free fatty acid goal was 0.07 mEq/g.
• the reaction reached completion 2.25 hours after Tmax was reached. With phosphorous acid as the catalyst the reaction reached completion 4.67 hours after Tmax was reached. This represents a 51.8% reduction in reaction time as compared to standard.
• Tallow fatty acid (194.0 g, 0.71 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (50.5 g, 0.42 mole) was added to the flask. The phosphorous acid was added at a loading level of 500 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 mL/min and 200 mL/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser.
• Tallow fatty acid (195.9 g, 0.71 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (51.5 g, 0.43 mole) was added to the flask. The zinc acetate was added at a loading level of 270 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 mL/min and 200 mL/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser.
• Tallow fatty acid (198.8 g, 0.72 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (52.2 g, 0.44 mole) was added to the flask. The zinc oxide was added at a loading level of 120 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 mL/min and 200 mL/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser.
• Tallow fatty acid (198.0 g, 0.72 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine ( 1.9 g, 0.44 mole) was added to the flask. The zinc oxide was added at a loading level of 960 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 150 mL/min and 200 mL/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser.
• Tallow fatty acid (799.5 g, 2.91 mole) was placed into a round bottom flask at 75°C, under a blanket of nitrogen. Methyldiethanolamine (209.5 g, 1.76 mole) was added to the flask. The zinc oxide was added at a loading level of 2200 ppm. The mixture was stirred and heated until a temperature of 175°C was reached. The nitrogen was regulated and subsurface sparged at a rate of between 1 0 mL/min and 200 mL/min. The pressure was one atmosphere. The water was condensed with the help of an air cooled condenser.
• a mixture of dimethylethanolamine (DMEA, 114.5 g, 1.29 mole), C12/C14 mixed fatty methyl ester (270 g 1.21 mole), and Vertec 2000 a Titanium catalyst (0.27 g) was added to a 4-neck flask fitted with a nitrogen sparge, a distillation column, a thermocouple, and a mechanical stirrer. The mixture was heated from 140°C to 152°C over 5 hrs. Conversion to the esteramine was determined by proton NMR to be 24%.

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